Cationic heterocyclic disazo dyes for textile fibers



P Patented sepfj ig} i ture, a his urea or bis urethane coupling component hav- 3,401,153 ing the formula CA'I'IONIC HETEROCYCLIC DISAZO DYES H J h G F b FORIEXTILlZFgiERS J Km t 'l h 1 1,

n is er and larence oates r. gspor l Tenn., assignors to Eastman Kodak (iompany, Roch: 5 B RSXOCN Z N R3 B (H) ester, N.Y., a corporation of New Jersey wherein all symbols are defined above and wherein the No Drawing. Filed Oct. 22, 1965, Ser. No. 502,428 I prime symbols are the same as the principal symbols, is

7 Claimscoupled with two equivalents of the diazonium salt of a heterocyclic compound having the formula 10 ABSTRACT OF THE DISCLOSURE N Cationic azo compounds containing two azolyl-azo- A-CNH: (III) indolyl moieties in which the nitrogen atoms of the indolyl v groups are joined together by certain bisurea or bisuref- A lsfdefinid above fi fi thane groups are useful as dyes for acrylonitrile polymer coup mg mac mu 0 a compoun 0 0mm a textile material. compound of Formula III has the nonquaternized form of the structure of Formula I wherein the principal and prime symbols represent the same structures. The coupl- This invention relates to novel heterocyclic azo coming reaction is conventional and and will be more fully pounds and, particularly, to novel cationic heterocyclic described in the examples set forth hereinafter. Upon azo dyes for synthetic fibers, yarns and fabrics. obtaining a compound having the structure of Formula The novel cationic heterocyclic azo compounds of the I in the nonquaternized form, the compound is quaterinvention are characterized by the general formula nized with an alkylating agent to provide the symmetri- A and A represent the same or different radical or group the reaction sequence is illustrated as follows:

which ring may be a Z-thiazole ring, a Z-benzothiazole pared by reacting two moles of an N-hydoxyalkylor N- ring, a 1,3,4-thiadiazole-2-yl ring or a benzimidazole aminoalkylindole having the formula ring and the like; R R represents a lower alkyl radical, e.g. methyl, or a benzyl radical; B-RQX (W) B represents an indolyl radical; R and R; represent the same or different alkyl radicals,

e.g. methyl, ethyl and the like or the same or different wherein the symbols are defined above, with one mole of a diisocyanate having the formula monocyclic carbocyclic aromatic radicals, e.g. phenyl OCNZNCO (V) or substituted phenyl such as tolyl and the like or comwher in Z is defined above, When X is oxygen, the his binations thereof; coupling component will be a urethane and when X is R and R' present straight or branched-chain lower NH, th his coupling component will be a urea.

alkylelle radical, -gylene, ethylene n t e i If it is desired that the dye be unsymmetrical in struc- X and X represent O-- or -NH- and may be e ture, a difierent method than that described above is used. same or different; To prepare the unsymmetrical heterocyclic azo dye, the Z represents alkylene. hexamethylene; y diazonium salt of a heterocyclic compound having the Phenylene, P'P y P' y y alkarylene, -5- structure of Formula III is coupled with. the indole derivmethylenebis (phenylene); arall ylene, e.g. tolylen ative of Formula IV. The monoheterocylic dye thus xylylene or naphthalene and the like; and prepared has the f l Y represents an anionic material, e.g. CH SO or Cm-Q-wm I and the like. wherein the symbols are defined above. By subsequently reacting the dye of Formula VI with a diisocyanate of The heterocyclic azo dyes of the invention are prepared Formula V, a product is obtained which has the formula by two principal methods. The choice of method is dependent on whether the desired dye is to be symmetrical or 7 i N Br unsymmetrical. I

If it is desired that the dye be symmetrical in struc- A-CN=N B RKXCONZ NCO (VII) reaction of the compound of Formula VIII :2 I Following the above procedure but substituting m-tolyla "second dye having the FormulaVI, a dye having the structure ene diisocyanate, the. following coupler. was obtained...

Y I 1 5 CaHoNHQONH ,The following examples will illustrate the preparation of representative coupling components and dyes prepared therefrom.

PREPARATION OF COUPLERS Coupler No. 1

' Following the above procedure but substituting p xylylene diisocyanate, the following coupler was obtained.

damnncoNHoHro =NHooNHomt Coupler N0. 2 Yield=82%, M.P'. 220-222 C.

Analysis.-C, 76.20 (76.70); H, 6.73 (6.40); mol. wt. 680 688).

All the other couplers used in the dyes of the invention were prepared asdescribed in the procedure illustrated above. If, in the above illustrations, a hydroxyalkyl indole is substituted, the bis coupling component is a urethane.

PREPARATION OF SYMMETRICAL DYES Example 1 A solution of nitrosyl sulfuric acid, prepared from 0.72 g. of NaNO and 5 ml. of cone. H was added to 107ml. of 1:5 acid (1 part propionic:5 parts acetic acid) below 20 C.'This solution was cooled to 2 C. and- 1 g. ofZ-aminothiazole was added portionwise keeping the temperature below 5 C. After a second portion of 10 ml. of 1:5 acid was added, the diazotization was completed by stirring at 3-5 C. for 2 hr. It'was then added to a cooled slurry of 3.75 g. of coupler No. 1

. above,,in 100 ml. :of 1:5 acid. The coupling mixture immediately turneddark red. .It was adjusted to' a-pH'of 4.5 by addition of solid ammonium acetate taking care that the temperature was held at 10 C. or below. After 2 hr. standing with intermittent stirring the dye was isolated by drowning in water, filtering, washing with water and allowing to air dry. The dried dye was dissolved in 30 ml. of dimethylsulfate by heating and thequaterni zatio'ni-was completed by heating at 9 5100 C. for"1i.5 hr'fThe red solution was dro wned" in 300inl f o f ether,

the solid "product was collected on'a' funnelpwash d ether and dried in a vacuum. It dyes Qrlon" and \l'eifelirf 5 6 red shades which exhibit excellent fastness to light washsolved in 12.6 ml. of water and 5.8 ml. of concentrated ing and sublimation. It has the formula: v sulfuric acid. This solution was cooled in an ice-salt bath CH3 CH3 H Example 2 and tested with nitrosyl sulfuric acid, made from 0.72 g.

If the coup! in Example 1 is replaced by 344 of of sodium nitrite and sulfuric acid. The diazotization was coupler No. 2 and the quaternization carried out as decomplete after Stimllg at for 1% The diaZO scribed inExample 1, then another red dye results which 90 was added to f p 1, dissolved, also dyes Orlon and Verel in fast red shades. It has the 1n acetic acid and cooled m an ice bath. The pH of the formula: v coupling mixture was adjusted to about 5 by the addition a 1 CH +4- If a purer sample is desired, the dye may be dissolved in of sodium acetate. After 1 hr. the coupling solution was water by warming, filtering and the dye precipitated by diluted to 1 l. by addition of water, and the solid collected additi n f In h Case the anion 0f the y is on a funnel, washed with water, and dried. The dried cake dide ion. I was heated in 40 ml. of dirnethyl sulfate at 95-100 C.

E p 3 40 for 1% hrs. This solution was cooled to 25 C. and poured.

If the coupler in Example 2 is replaced by coupler Slowly with good stirring into 350 ml. of ether. The dye No. 3, the following dye is obtained: was then collected, washed with ether, and dried in a vacu- CH3 oir H This dye imparts red shades to acrylic fibers whichexhibit um desiccator. This dye imparts red shades to acrylic very good fastness properties as regards light and wet fibers and has the following structure: treatment. t

GtHtNHCONEL-QQHi-Q-JINQGHNH.in

Example 4 All the dyes in the examples illustrated in Table I, be-

An amount of 1.5 g. of Z-aminobenzothiazole was dis 75 low, were prepared as described in the foregoing examples.

The table headings correspond to Forniula I, except that ylindole 'was added. After stirring and heating an hrs? A=A, R =R' etc. since'-these are symmetrical dyes. the orange solution wasdrowned in water and the solid TABLE I Exnple A R] R, a; X z t a Y Shade on Orlon 0. v

a OH; I C3H6- NH-- CHZSOI Red-violet.

(H3 V M V (I 9 N-- CH; CH; -c=H- NH-- A r Yellowish-oranget HG t I (I311: i0 135+ OH; CH: C|Hu- -.-NH- 4035- Q outset Redi 3 a .v v v \S/ v 2 I 4 1i N-- cm CH: C:Hl 0 Q '3 1 Orange,

a t 1 H t CH: -GH: u v

CHaS--C I I. Y 2

12 CH: CH: C:|Hi O Q Q CHISOI Violet.

CHaO s PREPARATION OF UNSYMMETRICAL DYES product isolated, washed with water and dried. This dye; cake was dissolved in ml. of dimethyl sulfate and Example 13 heated at 95-100 C." for 1.5 hr. The red 'solution was drowned in ether, the solid collected on a funnel, washed An amount of 1.99 g. of the dye prepared from 2-diwith ether and dried in vacuum. It dyes Orlon and Vere] a zob enzothiazole and 1-'y-aminopropyl-Z-phenylindole was in fast red shades. This dye hasthe forn ula;

$H3 CHa .Q s HG 1LT N=N- H11} N N-- I s v s l zcmsor Q (5 NHCONH aHe dissolved in 50 ml. of dimethylformamide, then 0.87 g. The unsymmetrical bis azo dyes illustrated by the exof tolylene 2,4diisocyanate was added. After stirring at amples in Table II, below, were prepared from the aproom ternperature for one-half hr. the solution was heated propriate heterocyclic azo dyes reacted stepwise with the and stirred at CfforZ hr; 1.75 'g. of the dye prediisocyanate indicated by the jirbcedure of Example 13. pared from Z-diazothiazole and l-v-aminopropyl-zphen- The column headings correspond to Fdrinula 1.

TABLE 11 Example A A R1 R: R: R: R:

14..-- N- 110- -o3H- -o=Ht- [I ll CH3 i HC---S- HC -S 15.--. HC- HC- OH; -ciH@- -ozHtn H CH: HCS- Hc-s- 16.-.. CH; -Ca H;- -o=Ht-" i" CH:

11... N om Q Q -o3 -c3H6-- HC-N- 01130 -s- CH3 18.--- Hi CH3 CH3 CH3 'f'C2H4 -crEu-; Hc-s- 5 Example No. X X Z i Y Color on Orlon 14 NH NH -cHi--cm- I Yellowlsh-red. t

15 NH NH Q-cm-Q- omsoi Red. p

16 NH NH -oH=-om- CHsSO4 Bluish-red.

17 NH NH CH2CH:- cmso. Red.

is o o -crn-- cmso. Red.

The cationic heterocyclic azo dyes of the invention can be used for dying synthetic polymer fibers, yarns and fabrics giving a variety of fast orange to red-violet shades when applied thereto by conventional dye methods. In general, the dyes have improved fastness, for example, to washing, gas (atmospheric fumes) and sublimation.

As described above, the present cationic heterocyclic'" azo dyes are characterized by a structure which is distinct from other known dyes. This distinctive structure imparts unexpected properties to the present dyes, especially when they are used for dyeing textiles, including improved brightness and fastness to light. Thus, the dyes of the invention can be expected to be superior to similar but distinct dyes when tested by methods such as described in the A.A.T.C.C. Technical Manual, 1964 edition, depending in part upon the particular dye used and the fiber being dyed.

Textile materials dyed by the cationic heterocyclic azo dyes of the invention are characterized by containing at least about combined acrylonitrile units and up to about 95% acrylonitrile units, and modified, for example, by 85-5% of vinyl pyridine units as described in US. Patents 2,990,393 (Re. 25,533) and 3,014,008 (Re. 25,- 539) or modified by 65-5% of vinylpyrrolidone units, for example, as described by US Patent 2,970,783,'or modified with 65-5% acrylic ester or acrylamide units as described in US. Patents 2,879,253, 2,879,254 and 2,838,- 470. Similar amounts of the other polymeric modifiers mentioned above are also useful. A preferred group of 70-95% by weight of a copolymer of from 30 to 65% by weight of vinylidene chloride or vinyl chloride and 70-35% by weight of acrylonitrile, and (B) 30-5% by 7 weight of a second polymer from the group consisting of 1) homopolymelrs of acrylamidic monomers of the formula wherein R is selected from the group consisting of hydrogen and methyl,'and R and R are selected from the group consisting of hydrogen and alkyl groups of 1-6 carbon atoms, (2) copolymers consisting of at least two of said acrylamidic monomers, and (3) copolymers consisting of at least 50% by weight of at least one of said acrylamidic monomers and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.

A particularly efficacious group of modacrylic polymers is an acetone soluble mixture of (A) 70-95% by weight of a copolymer of 30-65% by weight of vinylidene chloride and 70-35% by weight of acrylonitrile and (B) 30-5% by weight of an acrylamide homopolymer having the above formula wherein R R and R are as described above. Specific polymers of that group contain 70-95% by weight of (A) a copolymer of from 30-65% by weight 41 of vinylidene chloride and 70-35% by weight of acrylonitrile and (B) 305% by weight of a -lower-N-alkylacrylamide polymer such as poly-N-methacrylamide,

amount of 0.1 gram of dye is dissolved by warming in 5 cc. of methyl Cellosolve. A 2% aqueous solution of a non-ionic surfactant, such as Igepal CA (a polymerized ethylene oxidealkylphenol condensation product), is added slowly until a fine emulsion is obtained and then the dye mixture is brought to a volume of 200 cc. with warm water. Five cc. of a 5% aqueous solution of formic acid or acetic acid are added and then 10 grams of fabric made from an acrylic fiber is entered and, in the case of Orlon 42, the dyeing is carried out at the boil for one hour. In the case of materials made of Verel acrylic fiber the dyebath temperature should not exceed 90 C. in order to avoid damage to the fiber. The dyed material is then washed well with water and dried.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be etfected within the spirit and I scope of the invention as described hereinabove, and as defined in the appended claims. a

What we claim is:

1. A symmetrical or unsymmetrical azo compound 1 having the formula (CHQJNHC ONH 1-2 wherein A C- represents Z-thiazolyl, 2-benzothiazolyl, 6-meth0xy- 2-benzothiazolyl, 1,3,4-thiadiazol-2-yl, 5 -methy1thio 1,3,4-thiadiazol-2-yl, l-lower alkyl-2-benzimida'zolyl, 1-benzyl-2-benzimidazolyl, "l-lower alkyl-1,3,4triazol-2-yl, or l-benzyl-1,3,4-triazol-2-yl, wherein the nitrogen atom to which R is attached is at the 3- position;

R represents lower alkyl or benzyl;

R2 alnd R' each .represents methyl, ethyl, phenyl, or

to yl; I T

R and R each represents lower alkylene;

X and X each represents O-- or NH-;

Zrepresents alkylene having up to 6 carbon atoms,

phenylene, phenylene substituted with methyl, 4,4- bis(phenylene)' methylene, or 1,4-dimethylenephenylene; and

Y represents an anion.

2. A compound according to claim 1 wherein represents 2-thiazolyl or Z-benzothiazolyl; R represents lower alkyl; R and R3 each represent phenyl; and Z represents phenylene, phenylene substituted with methylenephenylene.

3. The compound CH3 CH3 1 y I N --N-N=N-- |k J IL J l zomso ((i1H2):NHQONH-Q-CHQrNHCONHKHL);

, v4. The compound 7 I 4 CH, A CH;

' 2CHaSO4" J QlC CHzNHC onngcrmf J 5. compound A M l e.

methyl, 4,4-bis(phenylene)methylene, or l,4-di-' 13 14 6. The compound T ZQ si f 1 7. The compound CHzCHgCH NHC ONH -NI-ICONHCHzCH CHa References Cited UNITED STATES PATENTS 3,271,383 9/1966 Yamaya et a1 260-15-8 CHARLES B. PARKER, Primary Examiner. D. M. PAPUGA, Assistant Examiner.

UNITED STATES. PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,401 ,158 September 10 1969 John G. Fisher et a1,

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Columns 1 and 2, lines 24 to 29, the formula should appear as shown below:

$1 I 1 N R 0 R N 2Y I ll I, -C-N=NB-R sXCNHZ-NH-C-X -R -B -N=NC A (I) Column 1, line 35 [III-diazonium" should read (III-diazonium) Column 3, line 1, "VIII" should read VII lines 3 to 10, the formula should appear as shown below:

Columns 5 and 6, in each of the formulas of Examples 1, 2 and 3, "2CH SO and "2CH SO should read 2CH SO Column 12, lines 25 to 56, the formula should appear as shown below:

CH I

I ll 5 l l (CH2)3NHCONH N O 2)5 zcrgsog same column 12, lines 57 to 67, the formula should appear as shown below:

- ZCI-I SO I 1E1 CH 'NHCONHCH en NHCONH 63H J Q 4 2 2 3 Signed and sealed this 10th day of March 1970a (SEAL) Attest:

EDWARD MQFLETCHERJRG I WILLIAM E; SCHUYLER, JRO Attesting Officer Commissioner of Patents 

